Adsorption heat pump and use of adsorbent as adsorbent for adsorption heat pump

ABSTRACT

An adsorption heat pump is provided in which water vapor can be efficiently adsorbed and desorbed using a heat source having a lower temperature than ones heretofore in use because the pump employs an adsorbent which has a large difference in water adsorption amount in adsorption/desorption and can be regenerated (release the adsorbate) at a low temperature. 
     The invention provides an adsorption heat pump which comprises an adsorbate, an adsorption/desorption part having an adsorbent for adsorbate adsorption/desorption, a vaporization part for adsorbate vaporization which has been connected to the adsorption/desorption part, and a condensation part for adsorbate condensation which has been connected to the adsorption/desorption part, wherein the adsorbent, when examined at 25° C., gives a water vapor adsorption isotherm which, in the relative vapor pressure range of from 0.05 to 0.30, has a relative vapor pressure region in which a change in relative vapor pressure of 0.15 results in a change in water adsorption amount of 0.18 g/g or larger.

TECHNICAL FIELD

The present invention relates to an adsorption heat pump employing aspecific adsorbent and use of the specific adsorbent as an adsorbent foran adsorption heat pump.

BACKGROUND ART

In an adsorption heat pump, the adsorbent having an adsorbate, e.g.,water, adsorbed thereon is heated to desorb the adsorbate in order toregenerate the adsorbent, and the adsorbent dried is cooled to atemperature to be used for adsorbate adsorption before being used foradsorbate adsorption again.

Absorption type heat pumps in which waste heat or heat having arelatively high temperature (120° C. or higher) is utilized as a heatsource for adsorbent regeneration have already come into practical use.However, since the heat obtained from cogeneration apparatus, fuelcells, cooling water for automotive engines, solar energy, or the likegenerally has a relatively low temperature of 100° C. or below, itcannot be utilized as a heat source for driving the absorption type heatpumps presently in practical use. It has been desired to effectivelyutilize low-temperature waste heat of 100° C. or lower, especially from60° C. to 80° C. In particular, there is a strong desire for thepractical use thereof in motor vehicles which generate waste heat inlarge quantities.

In adsorption heat pumps, the adsorption properties required ofadsorbents vary considerably depending on the temperatures of utilizableheat sources even though the heat pumps operate on the same principle.For example, the temperatures of higher-temperature-side heat sourcesare from 60° C. to 80° C. in the case of waste heat from gas enginecogeneration and from solid polymer type fuel cells and are from 85° C.to 90° C. in the case of cooling water for automotive engines. Thetemperatures of cooling-side heat sources also vary depending on theplaces where the apparatus is installed. For example, the cooling-sideheat source temperatures in the case of motor vehicles are temperaturesobtained with the radiators, while those in buildings, houses, and thelike are the temperatures of water-cooling towers, river water, etc.Namely, the operating temperatures for an adsorption heat pump are asfollows. In the case of installation in buildings or the like, thelower-side temperatures are from 25° C. to 35° C. and the higher-sidetemperatures are from 60° C. to 80° C. In the case of installation inmotor vehicles or the like, the lower-side temperatures are about from30° C. to 45° C. and the higher-side temperatures are about from 85° C.to 90° C. There is hence a desire for an apparatus capable of beingoperated even with a small temperature difference between thelower-temperature-side heat source and the higher-temperature-side heatsource so as to effectively utilize waste heat. An adsorbent to beapplied to such apparatus is also desired.

Typical adsorbents known as adsorbents for adsorption heat pumps arezeolite 13X and A-form silica gel.

Recently, zeolites are being investigated, such as a mesoporousmolecular sieve (e.g., FSM-10) synthesized using the micellar structureof a surfactant as a template (Japanese Patent Laid-Open No.178292/1997) and a porous aluminum phosphate molecular sieve for use asa desiccant material commonly referred to as AlPO₄ (Japanese PatentLaid-Open No. 197439/1999).

It has already been reported that the temperature dependence ofadsorption properties is important for the adsorbents for adsorptionheat pumps (Ragaku Kôgaku Ronbun-shû, Vol. 19, No. 6 (1993), pp.1165-1170). There is a report therein that SG3 (manufactured by FujiSilysia Ltd.) shows a large temperature dependence and SG1 (manufacturedby the same) does not.

Furthermore, it has been reported that the adsorption performance ofAlPO₄-5, which is a porous aluminum phosphate molecular sieve, dependson temperature. Specifically, the adsorption performance at 25° C. andthat at 30° C. are shown (Colloid Polym Sci, 277 (1999) pp. 83-88).Likewise, the temperature dependence of AlPO₄-5 has been reported;adsorption isotherms obtained in an adsorption process at 20° C., 25°C., 30° C., 35° C., and 40° C. are shown (Dai-16-kai Zeoraito KenkyûHappyô Kai Kôen Yokô-shû, p. 91; Nov. 21 and 22, 2000).

Use of various adsorbents in adsorption heat pumps is beinginvestigated. However, our investigations revealed that there is yetroom for improvement in adsorption performance so as to enableapplication to an apparatus capable of being operated even with a smalltemperature difference between the lower-temperature-side heat sourceand the higher-temperature-side heat source.

DISCLOSURE OF THE INVENTION

In order for an apparatus to sufficiently operate even when theatmosphere surrounding the adsorbent has relatively high temperatures,it is necessary to adsorb the adsorbate at a low relative vaporpressure. In order to reduce the size of an apparatus by reducing theamount of the adsorbent to be used, the amount of an adsorbate adsorbedonto and desorbed from the adsorbent should be large. Furthermore, inorder to utilize a low-temperature heat source for adsorbate desorption(adsorbent regeneration), it is necessary that the desorptiontemperature is low. Namely, it is important that an adsorbent for use inadsorption heat pumps is one which (1) adsorbs an adsorbate at a lowrelative vapor pressure (capable of high-temperature adsorption), (2)attains a large adsorption/desorption amount, and (3) is capable ofadsorbate desorption at a high relative vapor pressure (capable oflow-temperature desorption).

The invention has been achieved for the purpose of providing anefficient adsorption heat pump which employs an adsorbent capable ofadsorbate adsorption/desorption in a low-relative-vapor-pressure region.

Another object of the invention is to provide use of an adsorbentcapable of adsorbate adsorption/desorption in alow-relative-vapor-pressure region as an adsorbent for adsorption heatpumps.

Still another object of the invention is to provide an adsorption heatpump having practically effective adsorption performance.

The invention provides, in one aspect thereof, an adsorption heat pumpwhich comprises an adsorbate, an adsorption/desorption part having anadsorbent for adsorbate adsorption/desorption, a vaporization part foradsorbate vaporization which has been connected to theadsorption/desorption part, and a condensation part for adsorbatecondensation which has been connected to the adsorption/desorption part,wherein the adsorbent, when examined at 25° C., gives a water vaporadsorption isotherm which, in the relative vapor pressure range of from0.05 to 0.30, has a relative vapor pressure region in which a change inrelative vapor pressure of 0.15 results in a change in water adsorptionamount of 0.18 g/g or larger.

The invention further provides, in another aspect thereof, use of theadsorbent described above as an adsorbent for adsorption heat pumps.

In still another aspect thereof, the invention provides an adsorptionheat pump which comprises an adsorbate, an adsorption/desorption parthaving an adsorbent for adsorbate adsorption/desorption, and avaporization/condensation part for adsorbate vaporization/condensationwhich has been connected to the adsorption/desorption part,characterized in that the adsorbent comprises a zeolite containingaluminum, phosphorus, and a heteroatom in the framework structure.

In a further aspect thereof, the invention provides an adsorption heatpump which comprises (a) an adsorbate, (b) an adsorption/desorption parthaving an adsorbent for adsorbate adsorption/desorption, (c) avaporization part for adsorbate vaporization which has been connected tothe adsorption/desorption part, and (d) a condensation part foradsorbate condensation which has been connected to theadsorption/desorption part, characterized in that the adsorbentcomprises a zeolite containing aluminum, phosphorus, and silicon in theframework structure, and that the zeolite gives a ²⁹Si-NMR spectrum inwhich the integrated intensity area for the signals at from −108 ppm to−123 ppm is not more than 10% based on the integrated intensity area forthe signals at from −70 ppm to −123 ppm.

Furthermore, the present inventors directed attention to the fact thatin the adsorption/desorption parts of heat pumps, the operatingtemperature during adsorbate adsorption differs from that duringadsorbate desorption. The inventors made intensive investigations inview of the fact. As a result, they have found that a heat pump havingpractically useful adsorption performance is one employing an adsorbentin which the value of a specific difference in adsorption amountdetermined from (1) an adsorption isotherm obtained at anadsorption/desorption part temperature during adsorption operation and(2) a desorption isotherm obtained at an adsorption/desorption parttemperature during desorption operation is within a given range. Theinvention has been achieved based on this finding.

Namely, in still a further aspect thereof, the invention provides thefollowing.

An adsorption heat pump which comprises (a) an adsorbate, (b) anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, (c) a vaporization part for adsorbatevaporization which has been connected to the adsorption/desorption part,and (d) a condensation part for adsorbate condensation which has beenconnected to the adsorption/desorption part, characterized in that

(1) the adsorbent comprises a zeolite containing at least aluminum andphosphorus in the framework structure, and

(2) the adsorbent is a water vapor adsorbent having a region in whichthe adsorption amount difference as determined with the followingequation is 0.15 g/g or larger in the range in which the relative vaporpressure φ2 b during adsorption operation in the adsorption/desorptionpart is from 0.115 to 0.18 and the relative vapor pressure φ1 b duringdesorption operation in the adsorption/desorption part is from 0.1 to0.14:

Adsorption amount difference=Q2−Q1

wherein

-   -   Q1=adsorption amount at φ1 b as determined from a water vapor        desorption isotherm obtained at a temperature (T3) used for        desorption operation in the adsorption/desorption part    -   Q2=adsorption amount at φ2 b as determined from a water vapor        adsorption isotherm obtained at a temperature (T4) used for        adsorption operation in the adsorption/desorption part, provided        that    -   φ1 b (relative vapor pressure during desorption operation in the        adsorption/desorption part)=[equilibrium water vapor pressure at        the temperature of coolant (T2) cooling the        condenser]/[equilibrium water vapor pressure at the temperature        of heat medium (T1) heating the adsorption/desorption part]    -   φ2 b (relative vapor pressure during adsorption operation in the        adsorption/desorption part)=[equilibrium vapor pressure at the        temperature of cold (T0) generated in the vaporization        part]/[equilibrium vapor pressure at the temperature of coolant        (T2) cooling the adsorption/desorption part]    -   (wherein T0=5 to 10° C., T1=T3=90° C., and T2=T4=40 to 45° C.).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic view of an adsorption heat pump.

FIG. 2 is a water vapor adsorption isotherm (25° C.) for SAPO-34(manufactured by UOP LLC) in Example 1.

FIG. 3 is a ²⁹Si-MAS-NMR spectral chart for SAPO-34 (manufactured by UOPLLC) in Example 1.

FIG. 4 is a water vapor adsorption isotherm (25° C.) for the zeolite ofExample 2.

FIG. 5 is an Si-MAS-NMR spectral chart for the ²⁹zeolite of Example 2.

FIG. 6 is a water vapor adsorption isotherm (25° C.) for the zeolite ofExample 3.

FIG. 7 is water vapor adsorption isotherms for SAPO-34 (manufactured byUOP LLC) in Example 4 which were obtained in adsorption process at 40°C. and desorption process at 90° C.

FIG. 8 is water vapor adsorption isotherms for SAPO-34 (manufactured byUOP LLC) in Example 4 which were obtained in adsorption process at 45°C. and desorption process at 90° C.

FIG. 9 is a water vapor adsorption isotherm (25° C.) for the zeolite ofReference Example.

FIG. 10 is a ²⁹Si-MAS-NMR spectral chart for the zeolite of ReferenceExample.

FIG. 11 is a water vapor adsorption isotherm (25° C.) for A-form silicagel in Comparative Example 2.

FIG. 12 is a water vapor adsorption isotherm (30° C.) for ALPO-5 inComparative Example 3.

In the figures, numeral 1 denotes an adsorption column, 2 an adsorptioncolumn, 3 an adsorbate piping, 4 a vaporizer, 5 a condenser, 11 a heatmedium piping, 111 a cooling-water inlet, 112 a cooling-water outlet,113 a warm-water inlet, 114 a warm-water outlet, 115 a switching valve,116 a switching valve, 21 a heat medium piping, 211 a cooling-waterinlet, 212 a cooling-water outlet, 213 a warm-water inlet, 214 awarm-water outlet, 215 a switching valve, 216 a switching valve, 30 anadsorbate piping, 31 a control valve, 32 a control valve, 33 a controlvalve, 34 a control valve, 300 an indoor unit, 301 a pump, 41 acold-water piping (inlet), 42 a cold-water piping (outlet), 51 acooling-water piping (inlet), and 52 a cooling-water piping (outlet).

BEST MODE FOR CARRYING OUT THE INVENTION

The invention will be explained below in more detail.

<Structure of Adsorption Pump>

First, the structure of adsorption heat pumps will be explained usingthe adsorption heat pump shown in FIG. 1 as an example.

An adsorption heat pump is constituted mainly of: an adsorbate; anadsorption/desorption part (adsorption columns 1 and 2) which is packedwith an adsorbent capable of adsorbate adsorption/desorption and servesto transfer the heat generated by adsorbate adsorption/desorption to aheat medium (hereinafter the adsorption/desorption part is sometimesreferred to as adsorption columns); a vaporization part (vaporizer 4)which serves to take out the cold obtained by adsorbate vaporization;and a condensation part (condenser 5) which serves to release outwardthe heat obtained by adsorbate condensation.

The vaporizer 4 contains a coolant (water in this embodiment) and is ina hermetically sealed state, with the inside being nearly vacuum. Thisvaporizer 4 is equipped inside with a heat exchanger 43 for heatexchange between the coolant and a heat medium (in this embodiment, afluid obtained by mixing water with an ethylene glycol-based antifreeze)which has undergone heat exchange in an indoor unit 300 with the airblowing into the room.

The adsorption columns 1 and 2 have, disposed therein, a heat exchangerhaving an adsorbent adhered to the surface thereof or packed therein.The condenser 5 has, disposed therein, a heat exchanger 53 for coolingand condensing the vapor coolant (water vapor) released from theadsorption column 1 or 2 with a heat medium which has been cooled with,e.g., the outside air.

The adsorption columns 1 and 2, which are packed with an adsorbent, areconnected to each other by an adsorbate piping 30. This adsorbate piping30 has control valves 31 to 34 disposed therein. In the adsorbatepiping, the adsorbate is present in the state of the vapor of theadsorbate or in the form of a mixture of the liquid and vapor of theadsorbate.

To the adsorbate piping 30 have been connected the vaporizer 4 and thecondenser 5. The adsorption columns 1 and 2 have been connected inparallel arrangement to the vaporizer 4 and the condenser 5. Between thecondenser 5 and the vaporizer 4 is disposed a return piping 3 forreturning the adsorbate condensed by the condenser (preferablycondensate water resulting from regeneration) to the vaporizer 4.Numeral 41 denotes an inlet for cold water serving as a cooling outputfrom the vaporizer 4, and numeral 51 denotes a cooling-water inlet forintroducing cooling water into the condenser 5. Numerals 42 and 52denote a cold-water outlet and a cooling-water outlet, respectively. Thecold-water pipings 41 and 42 are connected to an indoor unit 300 forheat exchange with an indoor space (space to be air-conditioned) and toa pump 301 for circulating cold water.

A heat medium piping 11 and a heat medium piping 21 have been connectedrespectively to the adsorption column 1 and the adsorption column 2. Theheat medium pipings 11 and 21 have switching valves 115 and 116 andswitching valves 215 and 216, respectively, disposed therein. A heatmedium serving as a heating source or cooling source for heating orcooling the adsorbent in the adsorption columns 1 and 2 is caused toflow through the heat medium pipings 11 and 21, respectively. The heatmedium is not particularly limited as long as it can effectivelyheat/cool the adsorbent packed in the adsorption columns.

Warm water is introduced through an inlet 113 and/or inlet 213 byopening or closing switching valves (three-way valves) 115, 116, 215,and 216. The warm water introduced passes through the adsorption column1 and/or 2 and is then discharged through an outlet 114 and/or outlet214. Likewise, cooling water is introduced through an inlet 111 and/orinlet 211 by opening or closing the switching valves 115, 116, 215, and216, passes through the adsorption column 1 and/or 2, and is thendischarged through an outlet 112 and/or outlet 212.

The coolant piping which connects the vaporizer 4 to the adsorptioncolumns 1 and 2 and the coolant piping which connects the condenser 5 tothe adsorption columns 1 and 2 have control valves 31 to 34, which openor close the respective coolant pipings. These control valves 31 to 34,the pump 301 for heat medium circulation, and the three-way valves 115,116, 215, and 216 for controlling the flow of a heat medium arecontrolled by an electronic controller (not shown).

To the heat medium piping 11 and/or 21 have been connected an outdoorunit disposed so as to be capable of heat exchange with the outside air,a heat source which yields warm water, and a pump for heat mediumcirculation (all of these are not shown). The heat source is notparticularly limited, and examples thereof include cogenerationapparatus, such as automotive engines, gas engines, and gas turbines,and fuel cells. In the case of automotive use, preferred examples of theheat source include automotive engines and automotive fuel cells.

<Outline of Adsorption Heat Pump Operation>

The operation of the air conditioning system (adsorption heat pump)according to this embodiment will be outlined below. The pump 301 isoperated to circulate the heat medium through the indoor unit 300 andthe vaporizer 4 to thereby vaporize the liquid coolant (preferablywater) in the vaporizer 4. The heat medium is thus cooled to cool theair to be blown into the room. Simultaneously with this operation, thecontrol valves 31 to 34 and the three-way valves 115, 116, 215, and 216are switched so that either of the two adsorption columns 1 and 2 is inthe adsorption mode and the other adsorption column is in the desorptionmode (regeneration mode).

Specifically, in the case where the first adsorption column 1 is to beoperated in the adsorption mode and the second adsorption column 2 is tobe operated in the desorption mode, valve switching is conducted in thefollowing manner. The three-way valve 115 and the three-way valve 116are regulated so as to establish connection to the cooling-water inlet111 side and the cooling-water outlet 112 side, respectively, whilekeeping the control valve 31 open and the control valve 33 close.Simultaneously therewith, the three-way valve 215 and the three-wayvalve 216 are regulated so as to establish connection to the warm-waterinlet 213 side and the warm-water outlet 214 side, respectively, whilekeeping the control valve 32 close and the control valve 34 open.

As a result, the coolant (water vapor) vaporized in the vaporizer 4flows into the first adsorption column 1 and is adsorbed onto theadsorbent packed therein. During this adsorption, the temperature ofthis adsorbent is kept at around the temperature of the surrounding airwith the cooling water introduced through the inlet 111.

On the other hand, warm water heated by a heat source (or the drivingengine in the case of application to a vehicle) is supplied to thesecond adsorption column 2 through the warm-water inlet 213. As aresult, the adsorbent in the second adsorption column releases thecoolant which was adsorbed thereon in the adsorption mode. The coolant(water vapor) thus desorbed is cooled and condensed in the condenser 5for regeneration.

After the lapse of a given time period, the control valves 31 to 34 andthe three-way valves 115, 116, 215, and 216 are switched, whereby themodes of the first adsorption column 1 and second adsorption column 2can be shifted to the desorption mode and the adsorption mode,respectively. By repeating such switching at a given interval, acontinuous cooling operation can be conducted.

<Adsorbents>

One feature of the invention resides in the adsorbents used in theadsorption heat pumps.

<Adsorbent 1>

An adsorbent in the invention is an adsorbent which, when examined at25° C., gives a water vapor adsorption isotherm which, in the relativevapor pressure range of from 0.05 to 0.30, has a relative vapor pressureregion in which a change in relative vapor pressure of 0.15 results in achange in water adsorption amount of 0.18 g/g or larger, preferably 0.2g/g or larger. This adsorbent preferably is one in which that change inwater adsorption amount in the range of from 0.05 to 0.20 is 0.18 g/g orlarger, preferably 0.2 g/g or larger.

Adsorbates are adsorbed as vapors onto adsorbents. A preferred adsorbentis a material which undergoes a large change in adsorbate adsorptionamount in a narrow relative vapor pressure range. The reasons for thisare as follows. When such an adsorbent undergoing a large change inadsorption amount in a narrow relative vapor pressure range is used, theamount of the adsorbent necessary for obtaining the same adsorptionamount under the same conditions can be reduced and the adsorption heatpump can be operated even with a smaller temperature difference betweenthe heat source for cooling and the heat source for heating.

The preference for that property of an adsorbent will become apparentfrom the following investigation.

First, the operating vapor pressure range for an adsorption heat pump isdetermined by the desorption-side relative vapor pressure (φ1 a) and theadsorption-side relative vapor pressure (φ2 a). The values of φ1 and φ2can be calculated using the following equations. The range of from φ1 ato φ2 a is the relative vapor pressure range in which the pump can beoperated.

Desorption-side relative vapor pressure (φ1a)=[equilibrium vaporpressure (Tlow1)]/[equilibrium vapor pressure (Thigh)]

Adsorption-side relative vapor pressure (φ2a)=[equilibrium vaporpressure (Tcool)/[equilibrium vapor pressure (Tlow2)]

The symbols have the following meanings.

Thigh (Temperature of High-Temperature Heat Source):

-   -   Temperature of heat medium used for desorbing adsorbate from        adsorbent and thereby regenerating the adsorbent

Tlow1 (Temperature of Low-Temperature Heat Source):

-   -   Temperature of adsorbate in condensation part

Tlow2 (Temperature of Low-Temperature Heat Source):

Temperature of heat medium used for cooling regenerated adsorbent inpreparation for adsorption

Tcool (Temperature of Cold Generated):

-   -   Temperature of adsorbate in the vaporization part, i.e.,        temperature of cold generated

The equilibrium vapor pressure can be determined from temperature usingan equilibrium vapor pressure curve for the adsorbent.

Examples of the operating vapor pressure range in the case where theadsorbate is water are shown below. When the high-temperature heatsource temperature is 80° C. and the low-temperature heat sourcetemperature is 30° C., then the operating vapor pressure range (φ1 a-φ2a) is from 0.09 to 0.29. Likewise, when the high-temperature heat sourcetemperature is 60° C. and the low-temperature heat source temperature is30° C., then the operating relative water vapor pressure range (φ1 a-φ2a) is from 0.21 to 0.29. Furthermore, in the case where waste heat froman automotive engine is utilized for operating an adsorption heat pump,the high-temperature heat source temperature and the low-temperatureheat source temperature are estimated at about 90° C. and 30° C.,respectively, from a statement given in Japanese Patent Laid-Open No.2000-140625. In this case, the operating relative vapor pressure range(φ1 a-φ2 a) is from 0.06 to 0.29.

It can hence be thought that in the case where waste heat from gasengine cogeneration or from a solid polymer type fuel cell or automotiveengine is utilized for operating an adsorption heat pump, the operatingrelative vapor pressure range (φ1 a-φ2 a) is from 0.05 to 0.30,preferably from 0.06 to 0.29. Namely, a material undergoing a largechange in adsorption amount in this operating moisture range ispreferred. Consequently, it is preferred to use a material which changesconsiderably in adsorption amount in the relative vapor pressure rangeof usually from 0.05 to 0.30, preferably from 0.06 to 0.29.

For example, the case where a cooling power of 3.0 kW (=10,800 kJ/hr) isto be obtained with an adsorption heat pump is supposed. This value of3.0 kW is the cooling ability of air conditions for use in general motorvehicles. It is thought from investigations on the engine rooms ofvarious motor vehicles that the volume of an adsorption heat pump isdesirably up to 15 liter.

<<Adsorption Amount Difference>>

The weight of an adsorbent capable of being packed into a volume of 15liter or smaller is then determined.

The parts which should be mounted in the engine room include adsorptioncolumn main bodies, a vaporizer, a condenser, and control valves. It isnecessary that these parts are mostly united into an assembly having avolume of 15 liter or smaller. It is thought from our investigationsthat the vaporizer, condenser, and valves can be arranged in a spacevolume of 4.5 liter. Consequently, the volume of the adsorption columnmain bodies is about 10.5 liter or smaller. Since the percentage packingof adsorbents in adsorption columns and the bulk density of adsorbentsare usually about 30% and about 0.6 kg/liter, respectively, the weightof an adsorbent which can be packed (W) is about 10.5×30%×0.6=1.89 kg.

Properties required of adsorbents will be explained next.

The cooling power R of an adsorption heat pump is expressed by thefollowing equation A.

R=(W·ΔQ·η _(c) ·ΔH/τ)·η_(h)  (equation A)

In equation A, W represents the weight of the adsorbent packed into eachadsorption column (one side); AQ represents the equilibrium adsorptionamount amplitude which results under the conditions for adsorption anddesorption, i.e., the adsorption amount difference (Q2−Q1); η_(c)represents adsorption amplitude efficiency, which shows the proportionof the actual adsorption amplitude in the time between switchingoperations to the equilibrium adsorption amplitude ΔQ; ΔH represents thelatent heat of vaporization of water; τ represents the time periodbetween operations of switching to the adsorption mode or desorptionmode; and η_(h) represents heat mass efficiency for taking account ofthe heat mass loss caused by the temperature changes of the adsorbentand heat exchangers between the temperature of warm water and thetemperature of cooling water.

As stated above, R is 3 kW and W is 1.89 kg/2=0.95 kg. An investigationwhich was made previously by us revealed that an appropriate value of Tis about 60 seconds, and it has been found that the values of ΔH, η_(c),and η_(h) are 2,500 kJ/kg, 0.6, and 0.85, respectively. Consequently, ΔQis determined using equation (A).

$\quad\begin{matrix}{{\Delta \; Q} = {{{{R/W}/\eta_{c}}/\Delta}\; {H \cdot {\tau/\eta_{h}}}}} \\{= {{{{3.0/0.95}/0.6}/2500} \cdot {60/0.85}}} \\{= {0.149\mspace{14mu} {{kg}/{kg}}}}\end{matrix}$

Namely, the adsorbent to be used in the adsorption heat pump for motorvehicles is one having a ΔQ of 0.15 g/g or larger, preferably 0.18 g/gor larger, more preferably 0.20 g/g or larger.

Although the adsorbent was explained above on the assumption that theadsorption heat pump is applied to motor vehicles, it is a matter ofcourse that any adsorbent having the properties shown above can besufficiently applied to other applications including stationary use.

As a result of the investigations given above, the adsorbent for use inan adsorption heat pump of the invention has been determined.

The adsorbent which shows a water adsorption amount difference of 0.18g/g or larger when the relative vapor pressure changes by 0.15 in therange of from 0.05 to 0.30 is not particularly limited as long as itsatisfies the property requirement. However, zeolites are promisingmaterials. In zeolites, the pore volume, which contributes toadsorption, is governed by the framework density because zeolites arecrystalline. Zeolite 13X (framework density, 12.7 T/1,000 Å), which isan example of the zeolites having the lowest framework density, has amaximum adsorption amount of about 0.30 g/g. Consequently, when theadsorption amount as measured at the lower limit of relative vaporpressure of 0.05, which is specified in the invention, is larger than0.15 g/g, then it is impossible to obtain an adsorption amountdifference of 0.18 g/g. Therefore, the adsorption amount at a relativevapor pressure of 0.05, as determined from a water vapor adsorptionisotherm, is desirably 0.15 g/g or smaller, preferably 0.12 g/g orsmaller, more preferably 0.10 g/g or smaller, still more preferably 0.07g/g or smaller, and still further preferably 0.05 g/g or smaller.

<Adsorbent 2>

Another feature of an adsorbent in the invention resides in that theadsorbent is a water vapor adsorbent having a region in which theadsorption amount difference as determined with the following equationis 0.15 g/g or larger in the range in which the relative vapor pressure(φ2 b) during adsorption operation in the adsorption/desorption part isfrom 0.115 to 0.18 and the relative vapor pressure (φ1 b) duringdesorption operation in the adsorption/desorption part is from 0.1 to0.14:

Adsorption amount difference=Q2−Q1

wherein

-   -   Q1=adsorption amount at φ1 b as determined from a water vapor        desorption isotherm obtained at a temperature (T3) used for        desorption operation in the adsorption/desorption part        Q2=adsorption amount at φ 2 ^(b) as determined from a water        vapor adsorption isotherm obtained at a temperature (T4) used        for adsorption operation in the adsorption/desorption part,        provided that    -   φ1 b (relative vapor pressure during desorption operation in the        adsorption/desorption part)=[equilibrium water vapor pressure at        the temperature of coolant (T2) cooling the        condenser]/[equilibrium water vapor pressure at the temperature        of heat medium (T1) heating the adsorption/desorption part]    -   φ2 b (relative vapor pressure during adsorption operation in the        adsorption/desorption part)=[equilibrium vapor pressure at the        temperature of cold (T0) generated in the vaporization        part]/[equilibrium vapor pressure at the temperature of coolant        (T2)

cooling the adsorption/desorption part] (wherein T0=5 to 10° C.,T1=T3=90° C., and T2=T4=40 to 45° C.).

Although the adsorption amount difference for the adsorbent in theinvention is thus specified, a more preferred adsorbent satisfies therequirement which is specified under any of the following conditions (A)to (C).

(A) T0 is 10° C. and T2 is 40° C.

(B) T0 is 5° C. and T2 is 40° C.

(C) T0 is 10° C. and T2 is 45° C.

The adsorbent performance described above will be explained below byreference to FIG. 1.

First, an explanation is given on the case of FIG. 1 in which thecontrol valves 31 and 34 are closed and the control valves 32 and 34 areopened.

In this case, the adsorbent packed in the adsorption column 2 adsorbsthe water vapor supplied from the vaporizer 4 and thus heats up. Duringthis adsorption, the adsorption column 2 is cooled and deprived of heatby the heat medium (e.g., cooling water) which is passing through theheat medium pipes 211 and 21. The temperature of this heat medium(cooling water), which is supplied through the pipe 211 for cooling theadsorption column 2 (adsorption/desorption part), is referred to as T2.

On the other hand, the temperature of the vaporizer 4 is regulated forthe purpose of generating cold. The adsorption-side relative vaporpressure φ2 b in this operation is defined by the following equation.

Adsorption-side relative vapor pressure φ2b =[equilibrium water vaporpressure (T0)]/[equilibrium water vapor pressure (T2)]

-   -   Equilibrium water vapor pressure (T0): equilibrium water vapor        pressure at the temperature T0 of the vaporizer 4    -   Equilibrium water vapor pressure (T2): equilibrium water vapor        pressure at the temperature T2 of the heat medium in the        adsorption column 2

On the other hand, the adsorption column 1 during this operation is inthe desorption (regeneration) mode. The adsorbent packed in theadsorption column 1 is regenerated by a regenerating heat source(temperature of the heat medium for heating the adsorption/desorptionpart; this temperature is referred to as T1). The condenser 5 is cooledwith the cooling water supplied through the heat medium pipe 51 andthereby condenses water vapor. The desorption-side relative vaporpressure φ1 in this operation is defined by the following equation.

Desorption-side relative vapor pressure φ1 b=[equilibrium vapor pressure(T2)]/[equilibrium vapor pressure (T1)]

-   -   Equilibrium vapor pressure (T2): equilibrium vapor pressure at        the temperature of the condenser 5 (=equilibrium vapor pressure        at the temperature T2 of the heat medium in the adsorption        column 2)    -   Equilibrium vapor pressure (T1): equilibrium vapor pressure at        the temperature (T1) of the regenerating heat source in the        adsorption column 1

An important point here is that in an adsorption column, the temperatureduring adsorption differs from the temperature during desorption(regeneration). Consequently, in the invention, the adsorption amountdifference is determined from a desorption isotherm obtained at adesorption temperature and from an adsorption isotherm obtained at anadsorption isotherm. Specifically, it is calculated using the followingequation.

Adsorption amount difference=Q2−Q1

wherein

-   -   Q1=adsorption amount at φ1 b as determined from a water vapor        desorption isotherm obtained at a temperature (T3) used for        desorption operation in the desorption part    -   Q2=adsorption amount at φ2 b as determined from a water vapor        adsorption isotherm obtained at a temperature (T4) used for        adsorption operation in the adsorption/desorption part, provided        that    -   φ1 b (relative vapor pressure during desorption operation in the        adsorption/desorption part)=[equilibrium water vapor pressure at        the temperature of coolant (T2) cooling the        condenser]/[equilibrium water vapor pressure at the temperature        of heat medium (T1) heating the adsorption/desorption part]    -   φ2 b (relative vapor pressure during adsorption operation in the        adsorption/desorption part)=[equilibrium vapor pressure at the        temperature of cold (T0) generated in the vaporization        part]/[equilibrium vapor pressure at the temperature of coolant        (T2) cooling the adsorption/desorption part]    -   (wherein T0=5 to 10° C., T1=T3=90° C., and T2=T4=40 to 45° C.).

The adsorbent according to the invention has an adsorption amountdifference, as determined with the equation shown above, of 0.15 g/g orlarger, preferably 0.18 g/g or larger. The larger the adsorption amountdifference, the more the adsorbent is preferred. However, when availablematerial sources which satisfy such performance are taken into account,the adsorption amount difference is usually 0.50 g/g or smaller,practically 0.40 g/g or smaller, especially 0.35 g/g or smaller.

Specifically, the adsorption amount difference is determined throughmeasurements made, for example, under (1) conditions in which T0 is 10°C. and T2 is 40° C., (2) conditions in which T0 is 5° C. and T2 is 40°C., or (3) conditions in which T0 is 10° C. and T2 is 45° C. Theadsorption amount difference thus determined may be any value not below0.15 g/g.

The necessity of the adsorption amount difference of 0.15 g/g or largeris derived from the following investigation, which is made on thesupposition that the adsorption heat pump is applied to motor vehicles.

<<Adsorption Temperature, Description Temperature>>

First, an adsorption isotherm and a desorption isotherm are obtained atan adsorption temperature and a desorption temperature, respectively,because the adsorption amount depends on the temperature duringadsorption and the temperature during desorption as stated above.

During adsorption, the adsorption column is cooled with cooling water inorder to inhibit the column from being heated up by adsorption heat.Because of this, the temperature of the cooling water (T2) is almostequal to the adsorption temperature (T4). On the other hand, duringdesorption, the adsorption column requires desorption heat and thetemperature of warm water (T1) is equal to the desorption temperature(T3).

Incidentally, heat medium temperatures in the adsorption heat pump areas follows: (1) the warm-water temperature is about 90° C. because it isa temperature obtained with the engine-cooling water; (2) the coolingtemperature is about from 40° C. to 45° C. because it is a temperatureobtained by heat exchange with the outside air; and (3) the temperatureof cold water necessary for generating a cold wind is about from 5 to10° C. Namely, the cold-water temperature is about from 5 to 10° C. onthe assumption that the adsorption heat pump is applied to general motorvehicles in Japan. The cooling temperature is about 40° C. in Japan, andis about 45° C. in regions where the outside air temperature is high.

Consequently, the adsorption temperature (T4) is about from 40° C. to45° C. and the desorption temperature (T3) is about 90° C.

In the invention, the adsorption temperature and the desorptiontemperature are employed as indexes to adsorbent performance. Theadsorbent is one which satisfies the requirement that the adsorptionamount difference, as determined from at least one of adsorptionisotherms obtained at adsorption temperatures of from 40° C. to 45° C.and from a desorption isotherm obtained at a desorption temperature of90° C., is 0.15 g/g or larger.

<<Adsorption Amount Difference>>

The adsorption amount difference (0.15 g/g or larger) is determined inthe same manner as for adsorbent 1.

Although the adsorbent was explained above on the assumption that theadsorption heat pump is applied to motor vehicles, it is a matter ofcourse that any adsorbent having the properties described above can besufficiently applied to other applications including stationary use.

It is noted that the adsorption amount difference according to theinvention is satisfied in the range in which the relative vapor pressureduring adsorption operation φ1 b in the adsorption/desorption part isfrom 0.115 to 0.18 and the relative vapor pressure during desorptionoperation φ1 b in the adsorption/desorption part is from 0.1 to 0.14.This range roughly corresponds to the range of operating relative vaporpressures for adsorption heat pumps.

When the adsorbent has a region in which the adsorption amountdifference is 0.15 g/g or larger in the range in which φ1 b and +2b arefrom 0.115 to 0.18 and φ1 b is equal to or higher than φ2 b, then thisadsorbent is advantageous because the adsorption heat pump can beoperated therewith even under severe temperature conditions which havebeen thought to be unable to be used for operating adsorption heatpumps.

Adsorbent 2 described above is selected from zeolites containing atleast aluminum and phosphorus in the framework structure.

<Adsorbent Materials>

The adsorbents in the invention preferably are zeolites. Especiallypreferred is a zeolite containing aluminum, phosphorus, and a heteroatomin the framework structure. The zeolites here may be natural zeolites orartificial zeolites. Examples of the artificial zeolites include thealuminosilicates, aluminophosphates, and the like defined byInternational Zeolite Association (IZA).

Of the aluminophosphates, ALPO₄-5 is unsuitable for use as an adsorbentin the invention because it shows hydrophobic adsorption properties. Formaking this material suitable for use as an adsorbent in the invention,it is preferred to replace part of the aluminum and phosphorus with aheteroatom, e.g., silicon, lithium, magnesium, titanium, zirconium,vanadium, chromium, manganese, iron, cobalt, nickel, palladium, copper,zinc, gallium, germanium, arsenic, tin, calcium, or boron, in order toimpart hydrophilicity.

Preferred of those are zeolites formed by replacing part of the aluminumand phosphorus with silicon, magnesium, titanium, zirconium, iron,cobalt, zinc, gallium, or boron. Most preferred of these are zeolitesformed by replacement with silicon; this kind of zeolites are commonlycalled SAPO. The heteroatoms thus incorporated may be of two or morekinds.

A preferred aluminophosphate among the zeolites usable as adsorbents inthe invention is a zeolite which contains aluminum, phosphorus, and aheteroatom in the framework structure and in which the proportions ofthe atoms present are represented by the following expressions (1), (2),and (3):

0.001≦x≦0.3  (1)

(wherein x represents the molar proportion of the heteroatom in theframework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure);

0.3≦y≦0.6  (2)

(wherein y represents the molar proportion of aluminum in the frameworkstructure to the sum of aluminum, phosphorus, and the heteroatom in theframework structure);

0.3≦z≦0.6  (3)

(wherein z represents the molar proportion of phosphorus in theframework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure).Among the proportions of atoms present, the proportion of the heteroatomis preferably represented by the following expression (4):

0.003≦x≦0.25  (4)

(wherein x is as defined above)and more preferably represented by the following expression (5):

0.005≦x≦0.2  (5)

(wherein x is as defined above).

Preferred of the zeolites containing aluminum, phosphorus, and aheteroatom in the framework structure are ones in which the heteroatomis silicon atom and which give a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −108 ppm to −123 ppmis not more than 10% based on the integrated intensity area for thesignals at from −70 ppm to −123 ppm. That integrated intensity arearatio is more preferably 9.5% or less, especially preferably 9% or less.

Furthermore, the zeolites preferably are ones which give a 29Si-MAS-NMRspectrum in which the integrated intensity area for the signals at from−70 ppm to −92 ppm is not less than 25% based on the integratedintensity area for the signals at from −70 ppm to −123 ppm. Thatintegrated intensity area ratio is more preferably 50% or more.

The 29Si-MAS-NMR spectra in the invention are ones obtained by a methodin which a sample is stored in a water-containing desiccator at roomtemperature over a whole day and night to cause the sample to adsorbwater to saturation and this sample is examined under the followingconditions using tetramethylsilane as a reference material.

Apparatus: Chemagnetic CMX-400 Probe: 7.5 mm MAS Probe Resonancefrequency: 79.445 MHz Pulse duration: 5.0 microsecond Pulse series:single pulse Waiting time: 60 seconds Revolution speed: 4,000 rps

A ²⁹Si-MAS-NMR spectrum for a zeolite gives information about thecombined state of silicon in the zeolite. From the positions anddistribution of peaks, the combined state of silicon can be understood.

Although a preferred zeolite in the invention contains aluminum,phosphorus, and silicon, the silicon atoms in the zeolite are present asSiO₂ units. In a ²⁹Si-MAS-NMR spectrum, the peak appearing at around −90ppm is attributable to silicon atoms each bonded, through oxygen atoms,to four atoms other than silicon atoms. In contrast, the peak appearingat around −110 ppm is attributable to silicon atoms each bonded to foursilicon atoms through oxygen atoms. Namely, when a zeolite gives aspectrum in which the peak at around −110 ppm has a high intensity, thismeans that silicon atoms have gathered together, i.e., the silicon atomsin the zeolite are in a lowly dispersed state.

Zeolites giving such a spectrum tend to satisfy the requirementconcerning adsorption properties according to the invention. This may bebecause the dispersion of silicon influences the adsorption propertiesof the zeolites and a zeolite having high silicon dispersion exhibitsperformance especially suitable for adsorbents for adsorption heat pumpsas will be described later.

On the other hand, the zeolite to be used as an adsorbent in theinvention preferably is one having a framework density of from 10.0T/1,000 Å³ to 16.0 T/1,000 Å³. More preferred is a zeolite in which theframework density is in the range of from 10.0 T/1,000 Å³ to 15.0T/1,000 Å³. The term framework density herein means the number offramework-constituting elements other than oxygen per 1,000 Å³ of thezeolite; this value is governed by the structure of the zeolite.

Framework density correlates to pore volume. In general, when theframework density is high, the pore volume is small and this tends toresult in an insufficient adsorption amount and poor performance in useas an adsorbent for adsorption heat pumps. On the other hand, when theframework density is low, the volume of pores capable of adsorption islarge. Although this adsorbent has an increased adsorption amount, ittends to have a reduced density and poor strength.

Examples of zeolite structures satisfying the requirement concerningframework density include AFG, MER, LIO, LOS, PHI, BOG, ERI, OFF, PAU,EAB, AFT, LEV, LTN, AEI, AFR, AFX, GIS, KFI, CHA, GME, THO, MEI, VFI,AFS, LTA, FAU, RHO, DFO, EMT, AFY, and *BEA in terms of the code definedby IZA. Preferred examples thereof include AEI, GIS, KFI, CHA, GME, VFI,AFS, LTA, FAU, RHO, EMT, AFY, and *BEA. Preferred are zeolites havingthe structure CHA, AEI, or ERI. Especially preferred of these is thestructure CHA.

The structure of a zeolite is determined by obtaining an XRD patternthrough powder XRD (powder X-ray diffraction) and comparing this patternwith XRD patterns given in Collection Of Simulated XRD Powder PatternsFor Zeolites (1996, ELSEVIER).

Furthermore, the relationship between structure and framework density isdescribed in Atlas Of Zeolite Structure Types (1996, ELSEVIER), IZA.Framework density can hence be determined from the structure.

For example, the silicoaluminophosphate known as SAPO-34, which containsatoms of elements including silicon incorporated in the zeoliteframework structure, can be used as an aluminophosphate of the CHAstructure. Thus, desired adsorption performance can be imparted.

Although the adsorbents in the invention preferably are zeolitescontaining aluminum, phosphorus, and a heteroatom in the frameworkstructure, the zeolites may be aluminosilicates as long as they have theadsorbent properties described above. In this case, part of the siliconand aluminum (or with respect to the aluminum, all of it) in theframework may have been replaced with other atoms, e.g., magnesium,titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, zinc,gallium, tin, or boron. In case where aluminosilicates have too small asilicon/aluminum molar ratio, abrupt adsorption occurs in a region oftoo low humidities as in the case of zeolite 13X. In case where thatratio is too large, the aluminosilicates are too hydrophobic tosufficiently adsorb water. Consequently, the zeolite to be used in theinvention has a silicon/aluminum molar ratio of generally from 4 to 20,preferably from 4.5 to 18, more preferably from 5 to 16.

The zeolites described above include ones having cation speciesexchangeable with other cations. In this case, examples of the cationspecies include proton, alkali elements such as Li and Na, alkalineearth elements such as Mg and Ca, rare earth elements such as La and Ce,transition metals such as Fe, Co, and Ni, and the like. Preferred areproton, alkali elements, alkaline earth elements, and rare earthelements. More preferred are proton, Li, Na, K, Mg, and Ca. Thesezeolites may be used alone or used in combination of two or more thereofor in combination with another material such as silica, alumina, activecarbon, or clay.

The adsorbents in the invention have a pore diameter of preferably 3 Åor larger, especially 3.1 Å or larger. The pore diameter thereof ispreferably 10 Å or smaller, especially 8 Å or smaller, more preferably7.5 Å or smaller. In case where the pore diameter thereof is too large,there is the possibility that adsorption might not occur at desiredrelative humidities. In case where the pore diameter thereof is toosmall, molecules of water used as an adsorbate tend to less diffuse inthe adsorbent.

The adsorbents in the invention preferably have a heat of adsorption offrom 40 kJ/mol to 65 kJ/mol. This is because susceptibility todesorption also is an important property for adsorbents for adsorptionheat pumps in which it is required that desorption occurs with a heatsource of 100° C. or lower. Susceptibility to desorption is inverselyproportional to adsorption force. Consequently, the heat of adsorption,which is an index to the degree of adsorption, desirably is close to thelatent heat of condensation of water. The heat of adsorption for theadsorbents, which is not lower than the latent heat of condensation ofwater, may be 40 kJ/mol or higher. In case where the heat of adsorptionis too high, desorption with a heat source of 100° C. or lower tends tobe difficult. Consequently, a zeolite having a heat of adsorption notlower than the latent heat of condensation of water and not higher than65 kJ/mol is preferred. In this description, a differential heat ofadsorption was determined through simultaneous measurements ofadsorption amount and heat of adsorption (measuring temperature, 25° C.)by the method described in a document (Colloid Polym Sci, 277 (1999) pp.83-88), and the differential heat of adsorption for the adsorptionamount range of from 0.005 mol/g to 0.01 mol/g was taken as the heat ofadsorption.

An especially preferred example of the adsorbents for use in theinvention is SAPO 34, which is an SAPO (silicoaluminophosphate) in a CHAform (framework density=14.6 T/1,000 Å³).

Processes for producing the zeolite in the invention are notparticularly limited as long as the zeolite has the properties describedabove. For example, the zeolite can be produced in the following manneraccording to the method described in Japanese Patent Publication No.37007/1992, Japanese Patent Publication No. 21844/1993, Japanese PatentPublication No. 51533/1993, U.S. Pat. No. 4,440,871, etc. A method ofsynthesizing SAPO-34 is described in U.S. Pat. No. 4,440,871.

In particular, examples of processes for producing the preferred zeolitecontaining aluminum, phosphorus, and silicon atoms in the frameworkstructure include the following method.

First, an aluminum source, silica source, phosphate source, and templateare mixed together to prepare an aqueous gel.

As the aluminum source is used pseudoboehmite, aluminum isopropoxide,aluminum hydroxide, alumina sol, sodium aluminate, or the like.

As the silica source is used fumed silica, silica sol, colloidal silica,water glass, ethyl silicate, methyl silicate, or the like.

As the phosphate source is used phosphoric acid. Aluminum phosphate alsois usable.

As the template is used a quaternary ammonium salt such as atetramethylammonium, tetraethylammonium, tetrapropylammonium, ortetrabutylammonium, or a primary amine, secondary amine, tertiary amine,or polyamine, such as morpholine, di-n-propylamine, tripropylamine,triethylamine, triethanolamine, piperidine, cyclohexylamine,2-methylpyridine, N,N-dimethylbenzylamine, N,N-diethylethanolamine,dicyclohexylamine, N,N-dimethylethanolamine, choline,N,N′-dimethylpiperazine, 1,4-diazabicyclo(2,2,2)octane,N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine,3-methylpiperidine, N-methylcyclohexylamine, 3-methylpyridine,4-methylpyridine, quinuclidine,N,N′-dimethyl-1,4-diazabicyclo(2,2,2)-octaneion, di-n-butylamine,neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine,ethylenediamine, pyrrolidine, 2-imidazolidone, diisopropylethylamine, ordimethylcyclohexylamine.

The sequence of mixing an aluminum source, silica source, phosphatesource, and template varies depending on conditions. In general,however, a phosphate source is first mixed with an aluminum source, andthe resultant mixture is mixed with a silica source and a template. Thecomposition of the aqueous gel is generally such that 0.02<SiO₂/P₂O₅<20and 0.02<SiO₂/Al₂O₃<20, preferably such that 0.04<SiO₂/P₂O₅<10 and0.04<SiO₂/Al₂O₃<10, in terms of oxide molar ratio. The pH of the aqueousgel is from 5 to 10, preferably from 6 to 9.

Ingredients other than those shown above may suitably coexist in theaqueous gel. Examples of such ingredients include hydroxides and saltsof alkali metals or alkaline earth metals and hydrophilic organicsolvents such as alcohols.

The aqueous gel prepared is placed in a pressure vessel and held at agiven temperature, while being stirred or allowed to stand, under thepressure generated by the gel itself or under a gas pressure which doesnot inhibit crystallization. Thus, hydrothermal synthesis is conducted.

Conditions for the hydrothermal synthesis include a temperature ofgenerally from 100° C. to 300° C., preferably from 120° C. to 250° C.The reaction time is generally from 5 hours to 30 days, preferably from10 hours to 15 days.

After the hydrothermal synthesis, the reaction product is separated,washed with water, and dried. The organic matters contained therein areremoved by burning or another method to obtain a zeolite.

In the case where the zeolite is processed for use as a water vaporadsorbent, care should be taken not to reduce the adsorption performanceof the zeolite. In general, however, an inorganic binder such as aluminaor silica is used to mold the zeolite.

Silica gel, mesoporous silica, alumina, active carbon, clay, or the likemay be incorporated into the adsorbent besides the zeolite according tothe invention in order to impart desired water vapor adsorptionproperties to the adsorbent. However, from the standpoint of obtainingsatisfactory adsorption properties at low relative vapor pressures, theproportion of the zeolite in the adsorbent according to the invention isgenerally 60% by weight or higher, preferably 70% by weight or higher,more preferably 80% by weight or higher. From the standpoint ofadsorption properties, it is most preferred to use the zeolite alone asa water vapor adsorbent.

For application to an adsorption heat pump or the like, the adsorbent isused after being processed by a known method so as to have a givenstrength, particle diameter, and shape according to the application. Forexample, the size of adsorbent particles suitable for use in adsorptionheat pumps is about from 0.05 mm to 2 mm as disclosed in Japanese PatentLaid-Open No. 2001-38188. In the case where the adsorbent is bonded toan adsorption core with an adhesive as disclosed in Japanese PatentLaid-Open No. 2000-18767, it is necessary that the adsorbent particleshave such a strength that they do not break when mixed with the adhesiveand dispersed.

<Method of Operation>

A method of operating an adsorption heat pump is explained withreference to FIG. 1. In the first step, the control valves 31 and 34 areclosed and the control valves 32 and 33 are opened to thereby operatethe adsorption column 1 and the adsorption column 2 in the regenerationmode and the adsorption mode, respectively. Furthermore, the switchingvalves 115, 116, 215, and 216 are regulated to pass warm water andcooling water through the heat medium pipe 11 and heat medium pipe 21,respectively.

For example, in the case where the adsorption column 2 is to be cooled,cooling water which has been cooled by heat exchange with the outsideair, river water, or the like by means of a heat exchanger, e.g., acooling column, is introduced through the heat medium pipe 21 to coolthe adsorption column 2 usually to about 30 to 40° C. Furthermore, thecontrol valve 32 is opened and, as a result, the water present in thevaporizer 4 vaporizes and the resultant water vapor flows into theadsorption column 2 and is adsorbed onto the adsorbent. The movement ofwater vapor occurs based on the difference between the saturation vaporpressure at the vaporization temperature and the adsorption equilibriumpressure corresponding to the adsorbent temperature (generally from 20to 50° C., preferably from 20 to 45° C., more preferably from 30 to 40°C.). As a result, cold, i.e., a cooling output, corresponding the heatof vaporization is obtained in the vaporizer 4. The adsorption-siderelative vapor pressure φ2 a is determined from the relationship betweenthe temperature of cooling water for the adsorption column and thetemperature of the cold water yielded in the vaporizer (φ2 a is obtainedby diving the equilibrium vapor pressure of the adsorbate at thetemperature of the cold water yielded in the vaporizer by theequilibrium vapor pressure of the adsorbate at the temperature of thecooling water in the adsorption column). It is, however, preferred tooperate so that φ2 a is higher than the relative vapor pressures atwhich the adsorbent specified in the invention adsorbs a maximum amountof water vapor. This is because when φ2 a is lower than the relativevapor pressures at which the adsorbent specified in the inventionadsorbs a maximum amount of water vapor, then the adsorbing ability ofthe adsorbent cannot be effectively utilized, resulting in an impairedoperation efficiency. Although φ2 a can be suitably selected accordingto the ambient temperature, etc., the adsorption heat pump is operatedunder such temperature conditions that the adsorption amount at φ2 a isgenerally 0.20 or larger, preferably 0.29 or larger, more preferably0.30 or larger. This adsorption amount is determined from an adsorptionisotherm obtained at 25° C.

The adsorption column 1 in the regeneration mode is heated with warmwater of generally from 40 to 100° C., preferably from 50 to 98° C.,more preferably from 60 to 95° C., and comes to have an equilibriumvapor pressure corresponding to the temperature range shown above.Condensation thus occurs at the saturation vapor pressure at acondensation temperature of from 30 to 40° C. in the condenser 5 (thistemperature is equal to the temperature of the cooling water with whichthe condenser is being cooled). Water vapor moves from the adsorptioncolumn 1 to the condenser 5 and is condensed to water. The water isreturned to the vaporizer 4 through the return piping 3. Thedesorption-side relative vapor pressure φ1 a is determined from therelationship between the temperature of cooling water for the condenserand the temperature of warm water (φ1 is obtained by dividing theequilibrium vapor pressure of the adsorbate at the temperature of thecooling water for the condenser by the equilibrium vapor pressure of theadsorbate at the temperature of the warm water). It is, however,preferred to operate so that φ1 a is lower than the relative vaporpressers at which the adsorbent abruptly adsorbs water vapor. Althoughφ1 a can be suitably selected according to the ambient temperature,etc., the adsorption heat pump is operated under such temperatureconditions that the adsorption amount at φ1 a is generally 0.06 orsmaller, preferably 0.05 or smaller. Incidentally, the adsorption heatpump is operated so that the difference between the adsorbate adsorptionamount at φ1 a and the adsorbate adsorption amount at φ2 a is generally0.18 g/g or larger, preferably 0.20 g/g or larger, more preferably 0.25g/g or larger. The first step is conducted in the manner describedabove.

In the subsequent step as the second step, the control valves 31 to 34and the switching valves 115, 116, 215, and 216 are switched so as tooperate the adsorption column 1 and the adsorption column 2 in theadsorption mode and the regeneration mode, respectively, whereby cold,i.e., a cooling output, can be obtained from the vaporizer 4. Byalternately conducting the first and second steps described above, theadsorption heat pump is continuously operated.

An operation method was explained above with respect to an adsorptionheat pump having two adsorption columns. However, any desired number ofadsorption columns may be disposed as long as any of the adsorptioncolumns can be made to retain the state of being capable of adsorbingthe adsorbate by suitably desorbing the adsorbate adsorbed on theadsorbent.

Adsorption heat pumps utilize as a driving force the ability of anadsorbent to adsorb and release an adsorbate. Although water, ethanol,acetone, and the like can be used as the adsorbate in adsorption heatpumps, water is most preferred from the standpoints of safety, cost, andthe large quantity of latent head of vaporization.

The adsorption heat pumps of the invention employ an adsorbent capableof undergoing a large change in adsorption amount with a change inrelative vapor pressure in a narrow range. The adsorption heat pumps arehence suitable for use in applications where apparatus size reduction isrequired and adsorbent packing amounts are limited, such as, e.g., airconditioning systems for vehicles.

EXAMPLES

The invention will be explained below in detail by reference toExamples, but the invention should not be construed as being limited bythe following Examples in any way.

In the following Examples, water vapor adsorption isotherms at 25° C.were obtained by examining the adsorbents for water vapor adsorptionproperties under the following conditions.

-   -   Adsorption isotherm analyzer: Belsorb 18 (manufactured by Bel        Japan Inc.)    -   Temperature of high-temperature air chamber: 50° C.    -   Adsorption temperature: 25° C.    -   Initial pressure introduced: 3.0 Torr    -   Number of points for setting pressure introduced: 0    -   Saturated vapor pressure: 23.76 mmHg    -   Equilibrium time: 500 sec    -   Pretreatment: 300° C. 5-hour evacuation

A measurement for determining the differential heat of adsorption wasmade under the following conditions.

-   -   Measuring apparatus: calorimeter and adsorption amount-measuring        apparatus (manufactured by Tokyo Riko)    -   Temperature of measurement part: 25° C.    -   Temperature of thermostatic chamber for vapor introduction: 30°        C.

Example 1

A water vapor adsorption isotherm (25° C.) for SAPO-34 (manufactured byUOP LLC) is shown in FIG. 1. It can be seen from FIG. 1 that theadsorbent abruptly adsorbs water vapor at relative vapor pressures offrom 0.07 to 0.10, and that the change in adsorption amount in therelative vapor pressure range of from 0.05 to 0.20 is 0.25 g/g.

SAPO-34 is a CHA-form silicoaluminophosphate; the CHA form has aframework density of 14.6 T/1,000 Å3 and a pore diameter of 3.8 Å.

A ²⁹Si-MAS-NMR chart for SAPO-34 (manufactured by UOP LLC) is shown inFIG. 3. The spectral chart shows that the integrated intensity area forthe signals at from −108 ppm to −123 ppm and the integrated intensityarea for the signals at from −70 ppm to −92 ppm were 0.6% and 85.9%,respectively, based on the integrated intensity area for the signals atfrom −70 ppm to −123 ppm. Furthermore, the heat of adsorption was foundto be 58.6 kJ/mol.

Example 2

A CHA-form silicoaluminophosphate was produced in the following manneraccording to the method described in Japanese Patent Publication No.37007/1992.

To 18 g of water were gradually added 15.4 g of 85% phosphoric acid and9.2 g of pseudoboehmite (containing 25% water; manufactured by Condea).The resultant mixture was stirred. Ten grams of water was further addedthereto and this mixture was stirred for 1 hour. This liquid is referredto as liquid A. Separately from liquid A, a liquid was prepared bymixing 4.1 g of fumed silica (Aerosil 200), 11.6 g of morpholine, and 15g of water. This liquid was gradually added to liquid A. Thereto wasfurther added 24 g of water. This mixture was stirred for 3 hours.

The mixture obtained was introduced into a 200-cc stainless-steelautoclave containing a Teflon inner cylinder, and reacted by beingallowed to stand at 200° C. for 24 hours. After the reaction, thereaction mixture was cooled and the supernatant was removed bydecantation to recover the precipitate. The precipitate obtained waswashed with water three times, subsequently taken out by filtration, anddried at 120° C. This precipitate was burned at 550° C. for 6 hours inan air stream to obtain a zeolite.

Analysis by powder XRD revealed that this zeolite was a CHA-form(framework density=14.6 T/1,000 Å³) silicoaluminophosphate. Theframework density was determined from the structure by reference toAtlas Of Zeolite Structure Types (1996, ELSEVIER), IZA. A sample wasdissolved in an aqueous hydrochloric acid solution with heating and thissolution was subjected to ICP analysis. As a result, the proportions(molar proportions) of the aluminum, phosphorus, and silicon in theframework structure to the sum of these components were found to be asfollows: the proportion of silicon was 0.13, that of aluminum was 0.49,and that of phosphorus was 0.38.

An adsorption isotherm at 25° C. for this zeolite is shown in FIG. 4. Itcan be seen from FIG. 4 that this zeolite abruptly adsorbs water vaporat relative vapor pressures of from 0.07 to 0.10, and that the change inadsorption amount in the relative vapor pressure range of from 0.05 to0.20 is 0.25 g/g.

A ²⁹Si-MAS-NMR spectral chart for this zeolite is shown in FIG. 5. Inthis ²⁹Si-NMR spectrum, the integrated intensity area for the signals atfrom −108 ppm to −123 ppm and the integrated intensity area for thesignals at from −70 ppm to −92 ppm were 9.2% and 52.6%, respectively,based on the integrated intensity area for the signals at from −70 ppmto −123 ppm.

Example 3

To 128 g of water was added 72 g of aluminum isopropoxide. After themixture was stirred, 38.76 g of 85% phosphoric acid was added theretoand this mixture was stirred for 1 hour. To this solution was added 1.2g of fumed silica (Aerosil 200), followed by 89.3 g of 35% aqueoustetraethylammonium hydroxide (TEAOH). The resultant mixture was stirredfor 3 hours. This mixture was introduced into a 500-cc stainless-steelautoclave containing a Teflon inner cylinder, and reacted at 185° C. for60 hours with stirring at 100 rpm. After the reaction, the reactionmixture was cooled and the reaction product was separated bycentrifuging, washed with water, and dried at 120° C. This reactionproduct was burned at 550° C. for 6 hours in an air stream to obtain azeolite.

Analysis by powder XRD revealed that this zeolite was a CHA-formsilicoaluminophosphate (framework density=14.6 T/1,000 Å³). A sample wasdissolved in an aqueous hydrochloric acid solution with heating and thissolution was subjected to ICP analysis. As a result, the proportions(molar proportions) of the aluminum, phosphorus, and silicon in theframework structure to the sum of these components were found to be asfollows: the proportion of silicon was 0.03, that of aluminum was 0.50,and that of phosphorus was 0.47.

An adsorption isotherm at 25° C. for this zeolite is shown in FIG. 6. Itcan be seen from FIG. 6 that this zeolite shows an adsorption isothermsimilar to that of the zeolite of Example 2. Namely, this zeoliteabruptly adsorbs water vapor at relative vapor pressures of from 0.07 to0.10, and the change in adsorption amount in the relative vapor pressurerange of from 0.05 to 0.20 is 0.23 μg.

The heat of adsorption was 58.2 kJ/mol.

Example 4

SAPO-34 (manufactured by UOP LLC) was examined with an adsorptionisotherm analyzer (Belsorb 18, manufactured by Bel Japan Inc.). In FIG.7 is shown an adsorption-process water vapor adsorption isotherm at 40°C. for SAPO-34. The examination for adsorption isotherm was conductedunder the conditions of a high-temperature air chamber temperature of50° C., adsorption temperature of 40° C., initial pressure introduced of3.0 Torr, number of points for setting pressure introduced of 0,saturated vapor pressure of 55.33 mmHg, and equilibrium time of 500seconds.

On the other hand, a desorption-process adsorption isotherm was obtainedwith a gravimetric-method adsorption amount analyzer including amagnetic levitation balance (manufactured by Bel Japan Inc.) and,connected thereto, a vapor introduction part comprising a gas generationpart, pressure measurement part, and gas discharge part which weredisposed in a thermostatic air chamber. In obtaining adesorption-process adsorption isotherm, water vapor was discharged 50Torr by 50 Torr at a high-temperature air chamber temperature of 120° C.and a desorption temperature of 90° C. to determine the weight changes.The results are shown in FIG. 7.

On the assumption that the adsorbent is applied to an automotive airconditioning system for general motor vehicles, the conditions mayinclude T1=90° C., T2=40° C., and T0=10° C. It can be seen that undersuch conditions, the desorption-side relative vapor pressure φ1 and theadsorption-side relative vapor pressure φ2 are 0.11 and 0.17,respectively, and the difference in adsorption amount between φ1 and φ2is 0.21 g/g. This value is higher than the target adsorption amountdifference of 0.15 g/g. It can hence be seen that the automotive airconditioning system sufficiently functions in general motor vehicles.

When T1=90° C., T2=40° C., and T0=5° C., then the difference inadsorption amount between φ1=0.11 and φ2=0.12 is 0.20 g/g. This value ishigher than the target adsorption amount difference of 0.15 g/g. It canhence be seen that the air conditioning system sufficiently functions.

Furthermore, it is presumed that in some regions, the cooling watertemperature T2 increases to around 45° C. due to severe ambientconditions. Conditions for obtaining T0=10° C. when T1=90° C. in thiscase are investigated. Belsorb 18 was used to obtain anadsorption-process adsorption isotherm at 45° C. This isotherm is shownin FIG. 8 together with a desorption-process adsorption isotherm at 90°C. The examination for obtaining the adsorption isotherm at 45° C. wasconducted under the conditions of a high-temperature air chambertemperature of 65° C., adsorption temperature of 45° C., initialpressure introduced of 3.0 Torr, number of points for setting pressureintroduced of 0, saturated vapor pressure of 55.33 mmHg, and equilibriumtime of 500 seconds. In the case where T1=90° C., T2=45° C., and T0=10°C., then the desorption-side relative humidity φ1 is 0.14, which ishigher than the adsorption-side relative humidity φ2 of 0.13.

It can be seen that even in such a case in which the desorption-siderelative vapor pressure is higher than the adsorption-side relativevapor pressure, an adsorption amount difference of 0.16 g/g is obtainedwith the adsorbent of Example 4, which has a temperature dependence. Theadsorption heat pump employing the water vapor adsorbent of Example 4has proved to sufficiently work even in high-temperature regions.

REFERENCE EXAMPLE

To 173.4 g of water was added 115.3 g of 85% phosphoric acid. Theretowas gradually added 68 g of pseudoboehmite (containing 25% water;manufactured by Condea). This mixture was stirred for 3 hours. Theretowas added 30 g of fumed silica, followed by 87.2 g of morpholine and242.3 g of water. The resultant mixture was stirred for 4.5 hours. Thismixture was allowed to stand for aging at room temperature overnight.The mixture was then introduced into an induction stirring type 1-literstainless-steel autoclave containing a Teflon inner cylinder, andreacted at 200° C. for 24 hours with stirring at 60 rpm. After thereaction, the reaction mixture was cooled and the supernatant wasremoved by decantation to recover the precipitate. The precipitate thusobtained was washed with water, taken out by filtration, and dried at120° C. This precipitate was burned at 550° C. in an air stream toobtain a zeolite. Analysis by XRD revealed that this zeolite was in aCHA form. A sample was dissolved in an aqueous hydrochloric acidsolution with heating and this solution was subjected to ICP analysis.As a result, the proportions (molar proportions) of the aluminum,phosphorus, and silicon in the framework structure to the sum of thesecomponents were found to be as follows: the proportion of silicon was0.12, that of aluminum was 0.49, and that of phosphorus was 0.39.

An adsorption isotherm at 25° C. for this zeolite is shown in FIG. 9. Itcan be seen from FIG. 9 that this zeolite begins to abruptly adsorbwater vapor immediately after initiation of adsorption operation evenwhen the relative vapor pressure is still very low, and that the changein adsorption amount in the relative vapor pressure range of from 0.05to 0.20 is as small as 0.1 g/g or less. These results show that thiszeolite is unsuitable for use as an adsorbent for adsorption heat pumps.

This zeolite was subjected to Si-MAS-NMR analysis under the sameconditions, and the results thereof are shown in FIG. 10. In the²⁹Si-MAS-NMR spectrum, the integrated intensity area for the signals atfrom −108 ppm to −123 ppm and the integrated value for the signals atfrom −70 ppm to −92 ppm were 13.0% and 51.6%, respectively, based on theintegrated intensity area for the signals at from −70 ppm to −123 ppm.It can be seen from these results that even a CHA-formsilicoaluminophosphate is unsuitable for use as an adsorbent to beregenerated with a heat source of 100° C. or lower, when the peakappearing at around −110 ppm has a high intensity. The heat ofadsorption was 61.3 kJ/mol.

COMPARATIVE EXAMPLE 1

A mesoporous molecular sieve (FSM-10) shows an adsorption amountdifference as large as 0.25 g/g in the relative vapor pressure range offrom 0.20 to 0.35 (according to Japanese Patent Laid-Open No.178292/1997, FIG. 14, graph 4 for FSM-10). However, it shows a smalladsorption amount when the relative vapor pressure is in range of from0.05 to 0.30, which is an example of conditions for the operation of theadsorption heat pumps of the invention. In this range, the relativevapor pressure region where the adsorbent shows a large adsorptionamount change is from 0.15 to 0.30. However, the adsorption amountdifference in this region is 0.08 g/g, showing that this adsorbent haspoor performance in adsorption heat pumps.

COMPARATIVE EXAMPLE 2

A-form silica gel (manufactured by Fuji Silysia Chemical Ltd.), which isknown as an adsorbent suitable for adsorption heat pumps, was examinedwith an adsorption isotherm analyzer (Belsorb 18, manufactured by BelJapan Inc.) to obtain a water vapor adsorption isotherm at an adsorptiontemperature of 25° C. This isotherm is shown in FIG. 11. Thismeasurement was made under the same conditions as for the SAPO-34 inExample 1. The adsorption isotherm for A-form silica gel given in FIG.11 shows that over the relative vapor pressure range of from 0 to 0.7,A-form silica gel gives an adsorption amount nearly proportional to therelative vapor pressure. However, in the relative vapor pressure rangeof from 0.15 to 0.30, A-form silica gel shows an adsorption amountchange as small as 0.08 g/g like the mesoporous molecular sieve andporous aluminum phosphate molecular sieves. Although adsorption heatpumps employing a silica gel as an adsorbent have been marketed, theapparatus size should be large because of this small adsorption amountdifference.

COMPARATIVE EXAMPLE 3

In FIG. 12 is shown an adsorption isotherm for ALPO-5, which is AFI-form(framework density=17.5 T/1,000 Å³) zeolite as a porous aluminumphosphate molecular sieve (the isotherm is a quotation from ColloidPolym Sci, 277, pp. 83-88 (1999), FIG. 1 (adsorption temperature 30°C.)). The isotherm shows the following. ALPO-5 shows an abrupt increasein adsorption amount in the relative vapor pressure range of from 0.25to 0.40 and can be caused to adsorb and release the adsorbate in therelative vapor pressure range of from 0.05 to 0.3. However, theadsorption amount change in the relative vapor pressure range of from0.15 to 0.30 was as small as 0.14 g/g.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

This application is based on a Japanese patent application filed on Feb.21, 2001 (Application No. 2001-045677), Japanese patent applicationfiled on Apr. 10, 2001 (Application No. 2001-111902), Japanese patentapplication filed on Jun. 25, 2001 (Application No. 2001-191893), andJapanese patent application filed on Sep. 26, 2001 (Application No.2001-293990), the contents thereof being herein incorporated byreference.

INDUSTRIAL APPLICABILITY

One feature of the invention resides in that adsorbents having theproperties described above are used. These adsorbents can be used in theadsorption part of an adsorption heat pump. They give a large change inadsorption amount with a change in relative vapor pressure in a narrowrange. Consequently, these adsorbents are suitable for use in anadsorption heat pump in which the adsorbent packing amount is limited,for example, an air conditioning system for motor vehicles.

In the adsorption heat pumps of the invention, the adsorbents have alarge difference in water adsorption amount in adsorption/desorption andcan be regenerated (release the adsorbate) at a low temperature.Consequently, the adsorption heat pumps can be efficiently operated witha heat source having a lower temperature than ones heretofore in use.Furthermore, the adsorbents to be used in the invention show a largerchange in adsorption amount than the silica gels and zeolites heretoforein use in the same relative vapor pressure range. Consequently, theadsorption heat pumps can produce a higher dehumidifying effect when theadsorbents are used in almost the same weight.

Namely, with the adsorbents according to the invention, adsorption heatpumps capable of operating with a heat source having a relatively lowtemperature of 100° C. or below can be provided.

1-41. (canceled) 42: An adsorption heat pump which comprises anadsorbate, an adsorption/desorption part having an adsorbent foradsorbate adsorption/desorption, a vaporization part for adsorbatevaporization which has been connected to the adsorption/desorption part,and operates with a heat source of 100° C. or below, wherein theadsorbent, when examined at 25° C., gives a water vapor adsorptionisotherm which, in the relative vapor pressure range of from 0.05 to0.30, has a relative vapor pressure region in which a change in relativevapor pressure of 0.15 results in a change in water adsorption amount of0.18 g/g or larger. 43: The adsorption heat pump as claimed in claim 42,wherein the adsorbent comprises a zeolite having a framework density inthe range of from 10.0 T/1,000 Å³ to 16.0 T/1,000 Å³. 44: The adsorptionheat pump as claimed in claim 42, wherein the adsorbent has a porediameter of from 3 Å to 10 Å and a heat of adsorption of from 40 kJ/molto 65 kJ/mol. 45: The adsorption heat pump as claimed in claim 42,wherein the adsorbent is a zeolite containing at least aluminum,phosphorus, and a heteroatom in the framework structure. 46: Theadsorption heat pump as claimed in claim 45, wherein the zeolite is onein which the proportions of atoms present therein are represented by thefollowing expressions (1), (2), and (3):0.001≦x≦0.3  (1) wherein x represents the molar proportion of theheteroatom in the framework structure to the sum of aluminum,phosphorus, and the heteroatom in the framework structure;0.3≦y≦0.6  (2) wherein y represents the molar proportion of aluminum inthe framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure;0.3≦z≦0.6  (3) wherein z represents the molar proportion of phosphorusin the framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure. 47: The adsorption heat pump asclaimed in claims 45, wherein the heteroatom is silicon. 48: Theadsorption heat pump as claimed in claim 42, wherein the heteroatom issilicon and the zeolite gives a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −108 ppm to −123 ppmis not more than 10% based on the integrated intensity area for thesignals at from −70 ppm to −123 ppm. 49: The adsorption heat pump asclaimed in claim 48, wherein the zeolite gives a ²⁹Si-MAS-NMR spectrumin which the integrated intensity area for the signals at from −70 ppmto −92 ppm is not less than 25% based on the integrated intensity areafor the signals at from −70 ppm to −123 ppm. 50: The adsorption heatpump as claimed in claim 42, wherein the zeolite is one having thestructure represented by CHA in terms of the code defined byInternational Zeolite Association (IZA). 51: The adsorption heat pump asclaimed in claim 42, wherein the adsorbent has a zeolite content of 60%by weight or higher based on the whole adsorbent. 52: The adsorptionheat pump as claimed in claim 42, wherein the adsorbent, when examinedat 25° C., gives a water vapor adsorption isotherm in which theadsorption amount at a relative vapor pressure of 0.05 is 0.15 g/g orless. 53: An adsorption heat pump which comprises an adsorbate, anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, a vaporization part for adsorbate vaporizationwhich has been connected to the adsorption/desorption part, and acondensation part for adsorbate condensation which has been connected tothe adsorption/desorption part, and operates with a heat source of 100°C. or below, wherein the adsorbent is a zeolite containing aluminum,phosphorus, and a heteroatom in the framework structure. 54: Anadsorption heat pump which comprising (a) an adsorbate, (b) anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, (c) a vaporization part for adsorbatevaporization which has been connected to the adsorption/desorption part,and (d) a condensation part for adsorbate condensation which has beenconnected to the adsorption/desorption part, and operates with a heatsource of 100° C. or below, wherein the adsorbent is a zeolitecontaining aluminum, phosphorus, and silicon in the framework structure,and the zeolite gives a ²⁹Si-MAS-NMR spectrum in which the integratedintensity area of the signals at from −108 ppm to −123 ppm is not morethan 10% based on the integrated intensity area for the signals at from−70 ppm to −123 ppm. 55: An air conditioning system for vehicles whichemploys the adsorption heat pump as claimed in claim
 42. 56: A method ofoperating an adsorption heat pump comprising an adsorbate, anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, a vaporization pat for adsorbate vaporizationwhich has been connected to the adsorption/desorption part, and acondensation part of adsorbate condensation which has been connected tothe adsorption/desorption part, wherein the temperature of heat mediumused for desorbing adsorbate from adsorbent and thereby regenerating theadsorbent is 100° C. or lower and, Wherein the adsorbent is a watervapor adsorbent containing a zeolite, wherein the zeolite, when examinedat 25° C., gives a water vapor adsorption isotherm which, in therelative vapor pressure range of from 0.05 to 0.80, has a relative vaporpressure region in which a change in relative vapor pressure of 0.15results in a change in water adsorption amount of 0.18 g/g or larger.57: A method of operating an adsorption heat pump comprising anadsorbate, an adsorption/desorption part having an adsorbent foradsorbate adsorption/desorption, a vaporization part for adsorbatevaporization which has been connected to the adsorption/desorption part,and a condensation part for adsorbate condensation which has beenconnected to the adsorption/desorption part, wherein the temperature ofheat medium used for desorbing adsorbate from adsorbent and therebyregenerating the adsorbent is 80° C. or lower, and the temperature ofthe adsorbate in the condensation part is 30° C. or higher, Wherein theadsorbent is a water vapor adsorbent containing a zeolite, wherein thezeolite, when examined at 25° C. gives a water vapor adsorption isothermwhich, in the relative vapor pressure range of from 0.05 to 0.30, has arelative vapor pressure region in which a change in relative vaporpressure of 0.15 results in a change in water adsorption amount of 0.16g/g or larger. 58: The method of operating an adsorption heat pump asclaimed in claim 56 or 57, wherein the zeolite has a framework densityin a range of from 10.0 T/1.00 Å³ to 16.0 T/1.000 Å³. 59: The method ofoperating an adsorption heat pump as claimed in claim 56 or 57, whereinthe zeolite is a zeolite having a pore diameter of from 3 Å to 10 Å, anda differential heat of adsorption of from 40 kJ/mol to 65 kJ/mol. 60:The method of operating an adsorption heat pump as claimed in claim 56or 57, wherein the zeolite is a zeolite containing aluminum, phosphorus,and a heteroatom in the framework structure. 61: The method of operatingan adsorption heat pump as claimed in claim 60, wherein the zeolite isone in which the proportions of atoms present therein are represented bythe following expressions (1), (2), and (3):0.001≦x≦0.3  (1) wherein x represents the molar proportion of theheteroatom in the framework structure to the sum of aluminum,phosphorus, and the heteroatom in the framework structure;0.3≦y≦0.6  (2) wherein y represents the molar proportion of aluminum inthe framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure;0.3≦z≦0.6  (3) wherein z represents the molar proportion of phosphorusin the framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure. 62: The method of operating anadsorption heat pump as claimed in claim 60, wherein the heteroatom issilicon. 63: The method of operating an adsorption heat pump as claimedin claim 56 or 57, wherein the zeolite contains aluminum, phosphorus,and silicon in the framework structure, and the zeolite gives a²⁹Si-MAS-NMR spectrum in which the integrated intensity area for thesignals at from −108 ppm to −123 ppm is not more than 10% based on theintegrated intensity area for the signals at from −70 ppm to −123 ppm.64: The method of operating an adsorption heat pump as claimed in claim63, wherein the zeolite gives a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −70 ppm to −92 ppm isnot less than 25% based on the integrated intensity area for the signalsat from −70 ppm to −123 ppm. 65: The method of operating an adsorptionheat pump as claimed in claim 56 or 57, wherein the zeolite is onehaving the structure represented by CHA in terms of the code defined byInternational Zeolite Association (IZA). 66: The method of operating anadsorption heat pump as claimed in claims 56 or 57, wherein the zeolitecontent is 60% by weight or higher based on the whole adsorbent. 67: Themethod of operating an adsorption heat pump as claimed in claim 56 or57, wherein the zeolite gives a water vapor adsorption isotherm in whichthe water vapor adsorption amount at a relative vapor pressure of 0.05of 0.15 g/g or less. 68: A method of using an adsorbent which comprisesheating the adsorbent having an adsorbate with a heat source of 100° C.or lower to desorb the adsorbate, cooling the adsorbent dried to atemperature to be used for adsorbate adsorption, and again adsorbing theadsorbate, wherein the adsorbent, when examined at 25° C., gives a watervapor adsorption isotherm which, in the relative vapor pressure range offrom 0.05 to 0.30, has a relative vapor pressure region in which achange in relative vapor pressure of 0.15 results in a change in wateradsorption amount of 0.18 g/g or larger. 69: The method for using anadsorbent as claimed in claim 68, wherein the zeolite has a frameworkdensity in a range of from 10.0 T/1,000 Å³ to 16.0 T/1,000 Å³. 70: Themethod for using an adsorbent as claimed in claim 68, wherein thezeolite is a zeolite having a pore diameter of from 3 Å³ to 10 Å³, andhas differential heat of adsorption of from 50 kJ/mol to 65 kJ/mol. 71:The method for using an adsorbent as claimed in claim 68, wherein thezeolite is a zeolite containing aluminum, phosphorus, and a heteroatomin the framework structure. 72: The method for using an adsorbent asclaimed in claim 71, wherein the zeolite is one in which the proportionsof atoms present therein are represented by the following expressions(1), (2), and (3):0.001≦x≦0.3  (1) wherein x represents the molar proportion of theheteroatom in the framework structure to the sum of aluminum,phosphorus, and the heteroatom in the framework structure;0.3≦y≦0.6  (2) wherein y represents the molar proportion of aluminum inthe framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure;0.3≦z≦0.6  (3) wherein z represents the molar proportion of phosphorusin the framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure. 73: The method for using anadsorbent as claimed in claim 71 or 72, wherein the heteroatom issilicon. 74: The method for using an adsorbent as claimed in claim 68,wherein the zeolite contains aluminum, phosphorus, and silicon in theframework structure, and the zeolite gives a ²⁹Si-MAS-NMR spectrum inwhich the integrated intensity area for the signals at from −108 ppm to−123 ppm is not more than 10% based on the integrated intensity area forthe signals at from −70 ppm to −123 ppm. 75: The method for using anadsorbent as claimed in claim 74, wherein the zeolite gives a²⁹Si-MAS-NMR spectrum in which the integrated intensity area for thesignals at from −70 ppm to −92 ppm is not less than 25% based on theintegrated intensity area for the signals at from −70 ppm to −123 ppm.76: The method for using an adsorbent as claimed in claim 68, whereinthe zeolite is one having the structure represented by CHA in terms ofthe code defined by International Zeolite Association (IZA). 77: Themethod for using an adsorbent as claimed in claim 68, wherein thezeolite content is 60% by weight or higher based on the whole adsorbent.78: The method for using an adsorbent as claimed in claim 68, whereinthe zeolite gives a water vapor adsorption isotherm in which the watervapor adsorption amount at a relative vapor pressure of 0.05 to 0.15 g/gor less. 79: A method of using an adsorbent which comprises heating theadsorbent having an adsorbate with a heat source of 100° C. or lower todesorb the adsorbate, cooling the adsorbent dried to a temperature to beused for adsorbate adsorption, and again adsorbing the adsorbate,wherein the adsorbent is a zeolite containing aluminum, phosphorus, anda heteroatom in the framework structure. 80: A method of using anadsorbent which comprises heating the adsorbent having an adsorbate witha heat source of 100° C. or lower to desorb the adsorbate, cooling theadsorbent dried to a temperature to be used for adsorbate adsorption,and again adsorbing the adsorbate, wherein the adsorbent is a zeolitecontaining aluminum, phosphorus, and a heteroatom in the frameworkstructure, and the zeolite gives a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −108 ppm to −123 ppmis not more than 10% based on the integrated intensity area for thesignals at from −70 ppm to −123 ppm.